1

Kinetics

CHEMICAL KINETICS
Reminder

The following methods can be used to increase the rate of a reaction.

increase surface area
increase temperature
add a catalyst

use a light source (certain reactions only)

increase pressure (gaseous reactions only)
increase concentration

How they affect the rate has been studied in earlier

work with special reference to Collision Theory.

CONCENTRATION
Introduction

Increasing concentration = more frequent collisions = increased rate

However: Increasing the concentration of some reactants
can have a greater effect than increasing others.

Rate

Reactions start off at their fastest then slow as the reactant concentration drops.

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eg

In the reaction A + 2B > C

the concentrations might change as shown

the steeper the curve the faster the rate of the reaction
reactions start off quickly because of the greater likelihood of collisions
reactions slow down with time because there are fewer reactants to collide

Reactants (A and B)
Concentration decreases with time

Products (C)
Concentration increases with time

[]

[]

-3

refers to the concentration in mol dm

B
Time

the rate of change of

concentration is found from
the slope or gradient
the slope at the start will give
give the INITIAL RATE

[]

y
x

the slope gets less (showing

the rate is slowing down) as
the reaction proceeds

gradient = y
x

Time
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Kinetics

Investigation the variation in concentration of a reactant or product is followed with time

method depends on the reaction type and the properties of reactants/products

e.g.

Extracting a sample from the reaction mixture and analysing it by titration

Using a colorimeter or UV / visible spectrophotometer
Measuring the volume of gas evolved or a change in conductivity

THE RATE EQUATION

Format

links the rate of reaction to the concentration of reactants

can only be found by doing actual experiments, not by looking at the equation
the equation...

A + 2B + X > C + D

might have a rate equation like this

r = k [A] [B]2

rate of reaction
rate constant
concentration

units
units
units

conc. / time usually mol dm-3 s-1

depend on the rate equation
mol dm-3

Interpretation The above rate equation tells you that the rate of reaction is...
proportional to the conc of reactant A
proportional to the square of the conc of B
not proportional to the conc of X

doubling [A] - will double rate

doubling [B] - will quadruple rate
altering [X] - no effect on rate

Order of reaction
Individual order
Overall order

The power to which a concentration is raised in the rate equation

The sum of all the individual orders in the rate equation.
e.g.

and
Value(s)

in the rate equation

r = k [A] [B]2

the order with respect to A is 1

the order with respect to B is 2
the overall order is 3

1st Order
2nd Order
3rd Order

orders need not be whole numbers

orders can be zero if the rate is unaffected by how much substance is present

Remember The rate equation is derived from experimental evidence not by from an equation.
species in the stoichiometric equation sometimes arent in the rate equation
substances not in the stoichiometric equation can appear in the rate equation
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where r
k
[]

Kinetics

Q.1

State the overall order, and the individual orders, for the following ?
a) rate = k[C]3[D]
b) rate = k [Z]

Q.2

What substances appear in the rate, but not in the stoichiometric, equation ?

Experimental determination of order

Method 1

1. Plot a concentration/time graph

Calculate the rate (gradient) at points on the curve.
Select several concentrations
and find the rate (gradient of the
tangent) at each concentration.

CALCULATING THE RATE

4.0

4.0

3.0

3.5

rate = gradient = y / x
Concentration / mol dm -3

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Concentration / mol dm -3

3.5

2.5
2.0
1.5
1.0
0.5

3.0
2.5
2.0
1.5
1.0
0.5
0.0

0.0
0

10

20

30

40

50

60

10

20

30

40

50

60

Time / mins

Time / mins

When the concentration is 2.0 mol dm-3

the gradient
= - 3.2 mol dm-3
44 minutes
The gradient is negative because
the concentration is decreasing

Notice how the gradient gets less as

the reaction proceeds. This shows
that the rate of reaction is getting less.

rate = -7.3 x 10-2 mol dm-3 min-1

Concentration of reactant

CONCENTRATION v. TIME GRAPHS

WHAT TO LOOK FOR

A ZERO ORDER
a straight line with constant slope

B FIRST ORDER
downwardly sloping curve with a constant half life
C
B

C SECOND ORDER
steeper downwardly sloping curve; levels out quicker

Time
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Kinetics

Method 1
(cont)

2. Plot another graph of rate (y axis) versus the concentration (x axis)

A ZERO ORDER
a straight line horizontal to the x axis
rate is independent of concentration

Rate of reaction

B FIRST ORDER
a straight line with a constant slope
rate is proportional to concentration
GRADIENT = RATE CONSTANT (k)

B
C SECOND ORDER
an upwardly sloping curve; plotting
rate v. conc2 gives a straight line

Concentration

The initial rates method.

Do a series of experiments (at the same temperature) at different concentrations
of a reactant but keeping all others constant.
Plot a series of concentration / time graphs
Calculate the initial rate (slope of curve at start) for each reaction.
Plot each initial rate (y axis) against the concentration used (x axis)
From the graph, calculate the relationship between concentration and rate
Hence deduce the rate equation - see the graph at the top of the page
To find order directly, logarithmic plots are required.

Find the initial rate (gradient of

the tangent) at time = zero

4.0
3.5

Concentration / mol dm -3

3.0
2.5
2.0
1.5
1.0
0.5
0.0
0

10

20

30

40

Time / mins

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50

60

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Method 2

Kinetics

Half-life
( t )

A characteristics of a FIRST ORDER REACTION is that it has a constant half life

which is independent of the concentration. It is very similar to radioactive decay.

Definition

The time taken for the concentration of a reactant to drop to half of its original value.

Time taken for the concentration to drop from...

the time taken to drop...

1 to 1/2 = one half life
1/2 to 1/4 = one half life
1/4 to 1/8 = one half life
A useful relationship
k t = loge 2
= 0.693

4.0

Concentration / mol dm-3

from

4 mol dm-3 to 2 mol dm-3

2 mol dm-3 to 1 mol dm-3
1 mol dm-3 to 0.5 mol dm-3

3.5

17 min
17 min
17 min

3.0
2.5
2.0
1.5
1.0
0.5

= the half life

0.0
0

10

20

30

40

50

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Time / mins

TO CALCULATE THE RATE CONSTANT (k)

FOR A FIRST ORDER REACTION

k =

Q.3

0.693
t

In the reaction, A + B > X + Y, the concentration of A was found to vary as

shown in the table. It was later found that the order with respect to (wrt) B was 0.
plot a graph of [A] v. time

Time / s

[A] / mol dm

0
20

1.30
1.05

calculate the time it takes for [A] to go from...

1.30 to 0.65
1.00 to 0.50
0.50 to 0.25
(all in units mol dm-3)

40
60

0.85
0.68

80
100

0.55
0.45

deduce from the graph that the order wrt A is 1

120
140

0.36
0.29

calculate the value of the rate constant, k

160
180

0.24
0.19

200

0.15

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-3

60

Kinetics

Rate constant (k)

Value

Units

The units of k depend on the overall order of reaction.

e.g.

the value of the rate constant is affected by temperature

increasing the temperature increases the value of the rate constant
if k increases, so does the rate
an increase of 10C approximately doubles the rate of a reaction

if the rate equation is rate = k [A]2 the units of k will be dm3 mol-1 sec-1

Calculation Divide rate (conc per time) by as many concentrations that are in the rate equation
Overall Order
units of k
example

mol dm-3 sec-1

sec-1

dm3 mol-1 sec-1

in the rate equation r = k [A]

in the rate equation r = k [A] [B]2

dm6 mol-2 sec-1

k has units of sec-1

k has units of dm6 mol-2 sec-1

Derive suitable units for the rate constant k in the following rate equations.
r = k[C]3[D]
r = k [Z]2
r = k [A] [B]

Q.5
Expt
1
2
3
4
Hint

Using the data, construct the rate equation for the reaction between nitric
oxide and oxygen. What is the value and the units of the rate constant (k) ?
Initial [NO] / mol dm-3
1
2
2
3

Initial [O2] / mol dm-3

2
1
2
3

Initial rate / mol dm-3 s-1

7
28
56
?

Compare Expts. 2 and 3 to find the order with respect to O2

Compare Expts. 1 and 3 to find the order with respect to NO

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Q.4

Kinetics

The Arrhenius equation

Rate
Equation

a typical rate equation may like this r = k [A] [B]2

it shows how rate is affected by the concentrations of reactants [A] and [B]
the rate constant (k) shows how other variables affect the rate
a change of temperature or the addition of catalyst affects the value of k
it is expressed mathematically using the Arrhenius equation

-( )
Ea
RT

Arrhenius
equation
rate
constant

represents the fraction of the molecules in a gas

which have energies equal to or greater than the
activation energy at a stated temperature

includes factors like the frequency of

collisions and their orientation. It varies
slightly with temperature, although not much and
is taken as constant across small temperature ranges.

rate constant
temperature
gas constant
activation energy
constant
pre-exponential factor
(frequency factor)

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k
T
R
Ea
e
A

units depend on overall order

K
(K = C + 273)
8.13 J K-1 mol-1
J mol-1
2.71828
no units

Calculations values of A and Ea are obtained from the

Arrhenius equation by the relationship

ln

Ea
+ lnA
RT

is a logarithmic term ( loge NOT log10 )

(it can be obtained from a calculator)

convert and re-arrange the equation into the straight line formula y = mx + c
ln k =
y

(Ea R)

1T

ln A

y axis
x axis
gradient (m)
y intercept (c)

plot
plot
gives
gives

ln A

ln k
1T

- (Ea R)
ln A

ln k

Graphical
method

k = -

y
x

gradient (m) = y/c

1/T
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(K -1 )

Kinetics

Rate determining step

Explanation many reactions consist of a series of separate stages
each of these stages has its own rate and hence its own rate constant
the overall rate of a multi-step process is governed by the slowest step
- rather like a production line where the output can be held up by a slow worker
the slowest step is known as the rate determining step
investigation of the rate equation gives an idea of whether, or not, a reaction
takes place in a series of steps

Example

Iodine reacts with propanone...

CH3COCH3 + I2 > CH3COCH2I + HI

rate = k [CH3COCH3] [H+]

The rate equation for the reaction is

Why is [H+] in the rate equation?

the reaction is catalysed by acid

Why is [I2] not in the rate equation?

the reaction has more than one step and

the slowest step doesnt involve iodine

Example 2

The reaction

H2O2 + 2H3O+ + 2I > I2 + 4H2O

takes place in 3 steps

Step 1

H2O2 + I > IO + H2O

slow

Step 2

IO + H3O+ > HIO + H2O

fast

Step 3

HIO + H3O+ + I > I2 + 2H2O

fast

The rate determining step is STEP 1 as it is the slowest

Example 3

The reaction

2N2O5 > 4NO2 + O2

takes place in 3 steps

Step 1

N2O5 > NO2 + NO3

(occurs twice) slow

Step 2

NO2 + NO3 > NO + NO2 + O2

Step 3

NO + NO3 > 2NO2

from another Step 1

The rate determining step is STEP 1 as it is the slowest

The rate equation for the reaction is
rate = k [N2O5]
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fast
fast

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The rate determining step must therefore involve propanone and acid.

Kinetics

The hydrolysis of halogenoalkanes

Introduction

Haloalkanes (RX) are hydrolysed

by aqueous hydroxide ions

RX + OH(aq) > ROH + X

There are two possible mechanisms

Mech. 1

Mech 2

one step reaction

requires both species to collide
rate is affected by both reactants
second order overall

two step reaction

rate = k[RX][OH]

(i)

RX > R+ + X

(ii)

R+ + OH > ROH

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step (i) is slower as it involves

bonds breaking and will thus
be the rate determining step
rate depends only on [RX]
first order overall

rate = k[RX]

Mechanism 2 is very common with tertiary (3) haloalkanes whereas primary (1)
and secondary (2) haloalkanes usually undergo hydrolysis via a second order
process.

Molecularity

e.g.

The number of individual particles of the reacting species taking part

in the rate determining step of a reaction.
A + 2B > C + D
A > 2B

molecularity is 3 - one A and two Bs need to collide

however has a molecularity of 1 - only one A is involved

ln k = ln A -

Ea
RT

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